Bis-anthraquinonyl amides of azobiphenyldicarboxylic acid



BIS-ANTHRAQUINONYL AMIDES OF AZOBI- PHENYLDICARBOXYLIC ACID Joseph Deinet, Glassboro, N. J., assignor to E..I. du Pont de Nemours and Company, Wilmington, D,eI., a corporation of Delaware No Drawing. Application July 9, 1951,

Ser l. No- 235, 95

'6. (CL. ZHOZI).

O NH-din. which R stands for a vattable radical of the group, consisting of the unsubstituted anthraquinone, radical and the, anthraquinone radicals carrying a single monovalent substituent of the group consisting of halogen, methyl, carboxylic acid; and benzoylamino groups; the two anthraquinone nuclei being attached to the imino, groups in one of the positions alpha and beta, at least one of the anthraquinone nuclei carrying in a beta position a'single sulfo group of the formula SO3M in which M standsfor .H, .Na and -K'.

In U. S. Patent 2,228,455 a series of dianthraqu-inonyl amides containing azobiphenyl group are disclosed whichwhen applied as vat dyes have relatively good fastness properties but which are considerably weaker than the corresponding type of compounds when converted to theazole types, as more particularly disclosed in U. S. Patent 2,175,803. The dianthraquinonyl amide type dyes of U. S. Patent 2,228,455 further sufier from the defect that they are not suitable for application to textile materials by the usual vat printing processes since-they require excessive m for aging; nd hereforer sult n. weakand dull prints.

It is an object of thepresent invention to produce a class of yellow dyes in the anthraquinone vat dye series which;

2,719,842 Patented 4, 1955 v 2.

when they carry one or two sulfonic acid groups either as the free acid or more particularly as the alkali metal salts of such acids, dye and print cellulose materials by the usual vat dyeing and printing processes in strong, fast yellow shades, whereas compounds of similar formulae. which do not carry at least. one. sulfonic acid group are not-v satisfactory printing colors even when applied from print-- ing pastes. containing the usual printing assistant-s.

The compounds of this invention-may be prepared in a non-reactive medium by condensing an' aminoanthraquinone or an aminoanthra uinone-beta-sulfonic acid, either of which may carry a substituent ofthe group consisti'ng of halogen, methyl, -C0.0H1 ora benzoylamino group, with 4,4"-azo,biphenyl-4",4'"'-dicarboxylic acid chloride in substantially molar ratios, and then. further condensing the resulting mono acid'chl'oride in. situ with an aminoanthraquinone-beta-sulfonic acid or a halogen aminoanthraquinone-beta-sufionic acid at temperatures in the range of from 100 to 210 C. The products may be conditioned for dyeing or printing in the usual manner, such as by milling or acid pasting with or without purification with sodium hypochlorite. These new products are generally y,ellow pastes; they dye and print cotton or related fibers in bright shades. Their wet-fastness is of the same high order as found in most anthraquinone vat colors. Other fastness properties are in no way impaired by the; Presence: of: the; 8111f!) gI UP The following: examples are. given to illustrate the. in.-. vention. The parts usedareby weight,

Example. 1

' 5 80partsofnitrobenzene, 2 parts of pyridine, 35.5 parts of 2 -aminoanthraquinone-6-sulfonic acid sodium salt (fine powder) and parts of 4,4-azobiphenyl-4",4-dicarboxylic acid chloride areheated together, while agitating, at from 168 to- 1 70 C. andmaintained at this temperature for three hours. Aftercooling to 1'00 C. there are added 24.3 parts of l-aminoanthraquinone. Thereaction strong dyeings having good fastness properties. It is a 5 further object of the invention to provide strong, fast vat dyes in the yellow range which are particularly good as printing colors, being readily reduced in the printing gum and which are rapidly and completely fixed on the fiber during the aging process.

I hav f nd hat the thraqeinonx m des Qt he azobi henyldicarboxylic. acid. group. as, formulated above.

mass is then heated to 205- C. and maintained for threehours. It is then cooled to- 25- C., filtered, the filter cakewashed with nitrobenzene and alcohol} in turn, and, dried; The product is then acid pasted by drowni'ngin water a concentrated sulfuric acid solution of the color, thereafter filtered, washed acid-free and purified by bleaching with sodiumhypochlorite. It forms a bright yellow. paste and, dyes and prints cotton .or related fiber in bright yel lowshades of good fastness properties. The final product in the form of the sodium salt has the formula:

OOMMOUEJN Exampl'az- Ten hundred (1000) parts of nitrobenzene, 2 parts of pyridine, 55 parts of 4,4'-azobiphenyl-4",4'"-dicarboxylic acid and 43 parts of thionyl chloride are heated together ,to from 98 to 100 C. and maintained at this temperature for twenty hours. The mass is then air blown for one hour to remove excess of thionyl chloride. After cooling to 80-" (3., there are added 37.3 parts of 2-aminoanthraquinone-3-sulfonic acid sodium salt (fine powder) and the reaction mass is then heated to C. and maintained. atthis temperature for three'hours. The mass.- is' then cooled to. 25 C. and, after 25,-.6 parts; of 2;-amino.- anthraquinoneare added; it is heated to 208 C. andmaintained for three hours. It, is-thencooledto- 50 0., filtered 3 4 and the filter cake washed with nitrobenzene and alcohol, to 140 C. and maintained at this temperature for three in turn, and dried. The product is then acid pasted and hours. The mass is then cooled to 25 C. and 32.5 parts purified as in Example 1. It forms a bright yellow paste of Z-aminoanthraquinone-3-sulfonic acid (Na salt) fine and dyes and prints cotton in bright yellow shades of good powder are added and the temperature raised to 208 C. fastness properties. The product in the form of the so- 5 and maintained at this temperature for one and one-half dium salt has the formula: hours. The mass is then cooled to 50 C., filtered and O 0 It y W NHC N=N GHN SO3N8. ll ti Example 3 the filter cake washed with nitrobenzene and alcohol in Ten hundred (1000) parts of nitrobenzene, 2 parts of and Q The P d ct is then 361d pasted and pyridine, 55 parts of 4,4'-azobiphenyl-4",.4"'-dicarboxylic purlfied as 111 Example It forms a brlght yellow paste acid sodium salt and 43 parts of thionyl chloride are and y and Prints Cotton in bright Yellow shades of 89 heated together while agitating to 100 C. and mainfastness properties. The product in the form of the sotained at this temperature for twenty hours. The mass is dium salt has the formula:

O H 0 ll c r rrr- N=N -HN then air blown for one hour to remove excess of thionyl Example 5 chloride. The mass is thencooled to 50 C. and 38.5

parts of 2-am1noanthraqumone-3-sulfonic acid sodium pyridine 43 parts of 4y p y n,4ur di yli salt fine powder are added, the reaction mass is then heated o 3:- acid and 40 parts of thionyl chloride are heated together to 170 C. and maintained at this temperature for three 6 m 100 C. and maintained for fifteen hours. Then the and one-half hours. It is then cooled to 50 C. and 407 mass was air blown for one hour cooled to and arts of a normally occurring mixture of l-amino-S (and 1 8 )-benzoylaminoanthraquinones are added. The mass is after 27 Parts of l'ammoanthmqumonefll'carboxyhc Ten hundred (1000) parts of nitrobenzene, 2 parts of then heated to 210 C. and maintained at this temperature acid (fine Powder) are added it is heated to from f one and h 1f hours, ft which it is cooled to 5 40 165 C. and maintained for six hours at that temperature. C., filtered and the filter cake washed with nitrobenzene The mass is then cooled to and 325 Parts of and alcohol in turn, and dried. The product is then acid aminOanthraquinOne-3-S111f0nic acid vSodium Q pasted and purified as in Example 1. It forms a bright powder) are added and then the temperature raised to yellow paste and dyes and prints cotton or related fibers in 208 C. and maintained at this temperature for one and bright yellow shades of good fastness properties and one-half hours. The mass is then cooled to"40 C., filstrength. The product in the form of the sodium salt has tered and the filter cake washed with nitrobenzene and the formula: alcohol in turn, and dried. The product is then acid 0 it it NHO N=N- C-ITIH (I) SOsNa (B (5 or 8) I'VE ('30 Cum Example 4 pasted and purified as in Example 1. It forms a bright Eleven hundred (1100) parts of nitrobenzene, 2 parts Yellow Paste and dyes and Prints cotton in bright Yellow of pyridine, 43 parts of 4,4-a bi he y1-4",4' dicar shades of good fastness properties. ,The product in the boxylic acid and 40 parts of thionyl chloride are heated form of the sodium salt has the formula:

0 I I ll lfH-g N= C-HN N Boss together to 100 C. and maintained for fifteen hours. The mass is then air blown for one hour to remove excess of thionyl chloride and cooled to 25 C., then 26 parts of T611 hundred Parts of nitl'obellzene, 2 Parts of 1-amino-6-chloroanthraquinone are added and it is heated. pyridine, 43 parts of 4.4'-azobiphenyl- Y NaOOG Example 6 emanate acidand 40; parts: of: thionyl chlorideare heated to; 100! hours. The mass is then cooled 15025 C. and after 26 C; and maintained fiorrfiiteen hours; The mass is then parts of 1-chloror2-aminoanthraquinoneare added; itis cooled to; 25, C. and 2& parts of 1=aminoanfliraquinone heated to 140" C. and maintained at thistemperature for are added; The temperature. iSE raised/to. from 130! to six. hours.. The massis then cooled to 50" C. and 34.1 132, C. and maintained at this. temperature: for three parts of 1:-aminoanthraquinone-o-sulfonic acid potassium hours. The mass is. their cooled to 2'5f" Q, when. 34 salt (fine powder) are added and then heated": to 202 C. parts, of 1-aminoanthraquinone-6 (OJ-sulfonic; acid potasand maintained at this temperature for one and one-half sium salt (.fine powder) are: added, The: mass is then hours. It is.-then cooled to 50 C., filtered, and the'filter heated to 2700* C; and: maintained: at: this temperature cake washed with nitrobenzene andlalcohol' in turn, and for one and one-half hours:. It; is; then cooled; to 7036., 10 dried. The product is then acid pasted and? purified as filtered: and the cake washed with nitrobenzene and:- al.- in Example 1'. It: dyes andprints: in bright yellow shades coholinturn, and: dried. The product 'is: then acid of good fastness properties. and intthe form of/the sodium pasted and; purified: as; in Example. 1. It. forms: ahnight salt has. the. formula:

yellow paste and dyes and prints in bright yellow shades Example 9 of good fastness p e hevro mt n h f rm. f Ten hundred 1 000 parts or nitrobenzene, 2 parts of the sodiumsalt has. the formula:

pyridine, 43 parts of 4,4= -aZob iphenyl-4",4'-dicarboxy1ic Ii S.Q:NB) I I, SOaNa.

Example 7' acid. and '40 partsof thionyl chloride areheated together to 100 C. and maintained for one hour, then the mass Ten hundred (1000) parts of nitrobenzene, 2' parts of is air blown for onerhalfhour to remove excess ofthionyl' Pyridine, 43 P Of iph ny1- ",4"'- a xy1i chloride. The mass is then cooled" to 50 C. and after acid and parts of thionyl chloride are heated together 40 2213 par-ts of l -aminoanthraquinone areadded, it is to 100 C. and maintained for fifteen hours. The ma heated to: 130 C. andmai'ntained-at this temperature for is then cooled 5 n P f -CIiI three: hours. The mass is then cooled to 25- C. and aminoanthr quinone r ed. It is then e ted to after 3.6 parts.- of 1,-chloro-Zaminothraquinoner3-sul- 138" to 140 C. andmaintained at: this temperature for ionic acid,- sodium sa-lt (fine-powdery are; added, the mass.

six hours, then cooled to 25 C. and 32.5 parts of 2,- is heated to,2051.C g j mi d tthi temperature. aminoanthraquinone-3-sulfonic acid sodium salt, (fine fior one one-half hours. It: is then cooled-to C powder) are added; The mass is then heated to 205 C. filtered, the filter cake washed. with, nitrobenzene andv a1 and maintained at this temperature for one and one-half .cohol in turn, and dried. The product is then acid hours, then cooled to 50 C., filtered and the filter cake pasted and purified as in Example 1. It dyes and prints washed with nitrobenzene and alcohol in turn, and dried.. 50 eottontin bright yellow'shades of" good tastnesfs properties The product is then acid pasted and purified as in Bram .and in; the form of the sodium salt has the formula:

ple 1. It forms a bright yellow paste and dyes'andprints in bright yellow shades of good'fastness properties. The Example 10 product in the form of the sodium salt has the formula: Ten hundred 1000) parts of nitrobenzene, 2% parts 0 01 0- i I i 0' e -NH-i i -N=N --i HN 5 Naols I E Example 8 of pyridine; 43" parts of 4,4'-azobiphenyl-4",4'"-dicar- Ten hundred (1000) Parts; of nitmbenzene, 22 parts of boxylic, acid and 40 parts of thionyl chloride are heated pyridineAQ f: 4 4'aazobiphenyb4'"4";dica -b x ylic together to" C. and maintained for fifteen hours. acid and 40 parts of thionyl chloride are heated together e essy is then air blown for one hour to remove exto 100 C. and maintained at this temperature for fifteen cess of thionyl chloride. The mass is then cooled to 50 C. and 32.5 parts of Z-aminoanthraquinone-3-sulfonic acid sodium salt (fine powder) are added. It is then heated to from 170 to 175 C. and maintained for three hours. After cooling to 50 C., there are added 32.5 parts of a normally occurring mixture of l-aminoanthraquinone-6(7)-sulfonic acid sodium salt (fine powder) and the mass is then heated to 205 C. and maintained at this temperature for two hours. It is then cooled to 50 C., filtered and the filter cake washed with nitrobenzene and alcohol in turn, and dried. and purified as in Example 1. It forms a bright yellow paste and dyes and prints in bright yellow shades of good fastness properties. In the form of the sodium salt it has the formula:

in which the sulfo group is in the beta position.

Example 11 Ten hundred (1000) parts of nitrobenzene, 2 parts of pyridine, 43 parts of 4,4-azobiphenyl4",4"'-dicar- 45 boxylic acid and 40 parts of thionyl chloride are heated together to 100 C. and maintained for fifteen hours. The mass is then air blown for one hour to remove excess of thionyl chloride. It is cooled to 50 C. and-24 parts of lamino-Z-methylanthraquinone are added and then heated to 130 C. and maintained at this temperature for four hours. After cooling to 50 C. and adding 36 parts of a normally occurring mixture of l-aminoanthraquinone-6(7)-sulfonic acid sodium salt (fine powder), the mass is then heated to 205 C. and maintained at this temperature for one and one-half hours. It is then cooled to 50 C., filtered and the filter cake washed with nitrobenzene, alcohol and hot water in turn, and dried. The product is then acid pasted and purified as in Example 1. It forms a bright yellow paste and dyes and prints in yellow shades of good fastness properties, and in the form of the sodium salt it has the formula:

in which the sulfo group is in the beta positions.

As illustrated in the above examples, at least one of the anthraquinone nuclei may carry any of the substituents usually introduced into the anthraquinone nucleus in the preparation of anthraquinone vat dyes, such as halogen, methyl groups, benzoylamino groups and the carboxylic acid radical, the latter being illustrated more particularly in my U. S. Patent 2,601,100 of June 17, 1952. It will be obvious that, in place of the particular aminoanthraquinones which are employed in the above examples, isomeric compounds may be employed, that is, where the sulfonic acid group or the other substituents It is then acid pasted 1O are in various positions on the molecule, with the exception that the. compounds of this invention must carry the sulfonic acidgroup in a beta position on the anthraquinone nucleus. 1Amino-5-chloroanthraquinone, 1- amino-S-chloroanthraquinone, 1-amino-4-chloroanthraquinone may obviously be substituted for the 1-amino-6- chloroanthraquinone in Example 4. In the same manner, in Example 5, l-aminoanthraquinone-S-carboxylic acid (or the 8 isomer) may be substituted for the '1- aminoanthraquinone-6-carboxylic acid specifically disclosed. So, also, 1,3-dichlOrO-Z-aminoanthraquinone, 1,3dibromo-Z-aminoanthraquinone or l-bromo-Z-amino- 3-anthraquinone sulfonic acid and'similar compounds may be substituted for those specifically used in the condensation reactions of the above examples. The methylthioanthraquinoneamines such as l-methylthio-Z-aminoanthraquinone or the 1-amino-4(5 or 6)-methy1thioanthraquinones may likewise be used.

Since the dominating characteristic of the dyes of the molecules of this invention is the presence of at least one sulfonic acid group in a beta position on the anthraquinone nuclei of the bis-anthraquinonylamides of a20- biphenyldicarboxylic acid, it will be obvious that the simple monovalent substituents present on the same or on the other anthraquinone nucleus do not change the character of the resulting dyes.

I claim:

1. The anthraquinone vat dyes having the general formula:

0 NH EOO-E-HN.R

o Nn-EOQ-LBNOQ-E-nN o H i i 3. The anthraquinone vat ye of the formula: 10

NH-PJ N=N m r o mm 10 4. The anthraquinone vat dye of the formula:

NH 50 60H; 5. The anthraquinone vat dye of the formula:

6. The anthraquinone vat dye of the formula:

NH-EOUN: U g-I n 0 in which the second sulfo group is in the beta position.

References Cited in the file of this patent UNITED STATES PATENTS 2,108,126 Honold et a1 Feb. 15, 1938 2,145,954 Semple et a1. Feb. 7, 1939 2,228,455 Honold et a1 Jan. 14, 1941 2,395,229 Lowe et al. Feb. 19, 1946 2,601,100 Deinet June 17, 1952 OTHER REFERENCES Georgievics et al., Dye Chemistry, 1920, pages 6 and 7. 

1. THE ANTHRAQUINONE VAT DYES HAVING THE GENERAL FORMULA: 